Carbonate esters of hydroxy substituted fatty nitriles

ABSTRACT

Carbonate dinitriles of the formula:   WHERE N IS 5 TO 20, M IS 0 TO 15 AND THE SUM OF N AND M IS 14 TO 20. Diamines and diisocyanates derived therefrom with the latter being useful for preparing polymers.   D R A W I N G

United States Patent Robert C. Kuder Excelsior, Minn.;

Marwan R. Kamal, Dhahran, Saudi Arabia 819,438 I Apr. 25, 1969 Nov. 23,1971 General Mills, Inc.

[72] inventors [21 Appl. No. [22] Filed [45] Patented [73] Assignee [54]CARBONATE ESTERS 0F HYPROXY SUBSTITUTED FATTY NITRILES 8 Claims, NoDrawings [52] U.S.Cl 260/463, 260/18 TN, 260/67 TN, 260/75 NT, 260/77.5AP,

260/77.5 AT, l l7/l6l [Sl Int. Cl ..C07c 121/34, C07c 119/04, C08g 22/18[50] Field of Search 260/463 [56] References Cited UNITED STATES PATENTS2,265,814 l2/l94l Ritchie et al Primary Examiner lames 0. Thomas, Jr.Assistant Examiner-Diana G. Rivers Attorneys-Anthony A. Juettner,William C. Babcock and Gene 0. Enockson ABSTRACT: Carbonate dinitrilesof the formula:

II H(CH2)n( J(CH )mC'= N ful in same are set forth in Fatty Acids AndTheir Deriva- CARBONATE ESTERS OF HYDROXY SUBSTITUTED FATTY NITRILES Thepresent invention relates to new carbonate dinitriles. Moreparticularly, it relates to such carbonate dinitriles prepared fromcertain fatty compounds and phosgene.

The new carbonate dinitriles of the present invention have thestructural formula:

where n is5 to 20,m isOto l5,andthe sumofn andm is 14 to 20. it ispreferred that the sum of the whole integers n and m is l6. Our newcarbonate dinitriles are useful as intermediates (via the nitrilegroups) in the preparation of diacids, diesters. diamines, and the like.The diamines, for example, are useful for preparing diisocyanates whichin turn can be reacted with a variety of organic compounds containingtwo or more active hydrogen to yield polymers having utility ascoatings, moldings and the like.

The carbonate dinitriles of our invention can be prepared by thereaction of phosgene with a hydroxy substituted fatty nitrile. Thestarting hydroxy substituted fatty nitriles can be prepared in a numberof ways. One procedure is that set forth in VanderWal US. Pat. No.2,558,666 which shows the preparation of mixtures of such startingmaterials by the reaction of sulfuric acid under moderately lowtemperatures with unsaturated nitriles to form sulfates (sulfuricesters) which sulfates are then hydrolyzed to form the hydroxysubstituted fatty nitriles.

The preparation of mononitriles from fatty acids and ammonia is wellknown. This preparation and the conditions usereacted with phosgene toproduce the new carbonate dinitriles of the present invention. Suchphosgenation can be carried out by dissolving the hydroxy substitutedfatty nitriles in an organic solvent such as toluene, benzene, pyridine(also an acid acceptor) and the like or mixtures thereof followed by theslow addition of phosgene gas, preferably at temperatures below about 25C.i.e. 0 to 25 C.

The following examples are illustrative of the invention without beinglimiting.

EXAMPLEl To a solution of approximately equal parts of9-hydroxystearonitrile and lO-hydroxystearonitrile in 600 g. dry tolueneand 240 g. dry pyridine was added 124 g. phosgene gas over a period ofthree hours while maintaining the temperature at l5-20 C. The reactionmixture was allowed to wann to 25 C. over a period of 1 hour and thendiluted with water. The resulting top layer was separated, washed freeof pyridine and HCl, and stripped free of toluene on a rotaryevaporator, leaving 608 g. crude carbonate dinitrile. The

crude product was filtered to remove a small amount of white solid andthen further stripped in a falling-film molecular still to remove asmall amount of unreacted hydroxystearonitrile. The resulting productcontained 4.72 percent nitrogen (theoretical is 4.7 percent) andcomprised a mixture of position isomers having the formulas and ll Suchmixture of position isomers can be separated (as well as the isomers ofthe examples to follow) such as by chromatography. However, there isordinarily no reason to do so since the compounds are functionallyequivalent.

EXAMPLE ll and l li- EXAMPLE in Example I is essentially repeated usingthe mixture of 11- and 12-hydroxy substituted mononitriles obtained fromvaccenic acid. The resulting dinitriles have the formulas As indicatedabove, our new dinitriles are particularly useful for preparing diaminesand then diisocyanates. The diisocyanates find use in the preparation ofpolymers by reaction with organic compounds containing active hydrogens.

The dinitriles are converted to the diamines by hydrogenation. Thehydrogenation is carried out in the presence of ammonia utilizing ahydrogenation catalyst such as Raney cobalt or Raney nickel. Thediamines are then converted to the diisocyanates by the conventionalprocedure of reacting phosgene EXAMPLE A A mixture of 107 g. of thecarbonate dinitrile as prepared in Example I, 107 g. methanol, 16.2 g.Raney active cobalt catalyst and 80 ml. liquid ammonia was heated in astirred autoclave for 3.75 hours at 145-50 C. under hydrogen atl.980-2,460 p.s.i. The reaction mixture was then cooled to roomtemperature, filtered and stripped free of solvent in a rotaryevaporator. The resulting crude product (103 g.) was a light brown solidmelting over the range of 4262 C. This product was purified bydistillation through a falling-film molecular still to give a lightyellow solid melting at 54-69 C.. with an amine number of 189(theoretical amine number 188). The product comprised a mixture ofposition isomers having the formulas and EXAMPLE B Example 'A isessentially repeated using the mixture of dinitriles of example II. Theresulting carbonate diamines have the same formulas as the dinitrilesexcept that the C N groups are replaced by --CH,NH, groups.

EXAMPLE C Example A is essentially repeated using the mixture ofdinitriles of .example Ill. The resulting carbonate diamines have thesame formulas as the dinitriles except the -C N groups are replaced byCH NH, groups.

The following examples are illustrative of the preparation of thediisocyanates without being limiting.

EXAMPLE D To a solution of 205 g. phosgene in 700 ml. dry xylene at 18C. was added a solution of 188 g. carbonate diamine as 45 prepared inexample A in 300 ml. dry xylene over a period of 20 minutes. During thistime, the reaction temperature increased to C. and a precipitate(presumably the amine hydrochloride) formed in the reaction mixture. Thetemperature was increased to 112 C. in 3 1 hours. More phosgene was thenbubbled through the reaction mixture while the temperature was increasedover an hour to 130 C., at which point the mixture became clear. Thephosgene flow was then replaced by nitrogen and the xylene distilled offto a pot temperature of 200 C. at atmospheric pressure. The residue washeld at 200 C. for an hour under full vacuum of a water aspirator. Theresulting dark brown crude product was distilled through a falling-filmmolecular still at a jacket temperature of 260 C. to give a light yellowliquid product partially crystalline at room temperature. Analysis andinfrared spectrum showed that the product had a nitrogen content of 4.28percent (theoretical 4.32 percent), an NCO content of 1 1.72 percent(theoretical 12.99 percent) and absorption maxima at 4.42;. p.( NCO).5.77p. (carbonate C=O) and 7.91:.

(carbonate C-O). lt comprised a mixture of position isomers of theformulas and have the same formulas as the diamines except that the CH,NH groups are replaced by -CH NCO groups.

EXAMPLE F Example D is essentially repeated using the mixture ofdiamines of example C. The resulting carbonate diisocyanates have thesame fonnulas as the diamines except that the CH NH groups are replacedby -CH NCO groups.

As indicated above the diisocyanates are particularly valuable for thepreparation of polymers by reaction with compounds bearing at least twoactive hydrogen atoms as determined by the Zerewitinoff method. TheZerewitinoff test is described by Kohler in J. Am. Chem. Soc., 49, 3l8l(1927). Such polymers are useful especially as coatings for a variety ofsubstrates.

In general, the active hydrogen atoms of compounds reactive with thediisocyanates are attached to carbon, oxygen, nitrogen or sulfur atoms.Compounds containing the following groups will have active hydrogenatoms: primary amino, secondary amino, carboxyl, diazoamino, hydrazino,hydrazo, hydrazono, hydroxyamino, hydroxyl imido, imino, and mercapto.Most often these active hydrogen atoms are attached to oxygen, nitrogen,or sulfur atoms; thus they will be a part of groups such as OH. -SH, NH,NH CO;H, CONH --CONHR where R represents an organic radical, SO OH, -SONH and --CSNH Examples of suitable types of compounds include water,hydrogen sulfide, ammonia. hydroxyl polyesters, polyhydric polyalkyleneethers, polyhydric polythioethers, polyacetals, aliphatic polyols,including alkane, alkene and alkyne diols, triols, tetrols and the like,aliphatic thiols including alkane, alkene and alkyne thios having two ormore -SH groups; polyamines including both aromatic, aliphatic andheterocyclic diamines, triamines, tetramines and the like; as well asmixtures thereof. Of course, compounds which contain two or moredifferent groups within the above-defined classes may also be used suchas, for example, amino alcohols which contain an amino group and ahydroxyl group, amino alcohols which contain two amino groups and onehydroxyl group, aminoacids and the like.

Further illustrative classes and specific organic compounds I containingactive hydrogen atoms useful for preparing polymers are describedimmediately hereinbelow.

Any suitable polyester may be used and may contain tervminal hydroxylgroups, terminal carboxylic acid groups,

amino groups or the like. Moreover, the polyester may be a polyesteramide which was prepared by condensing an amino alcohol containing bothfree amino groups and free hydroxyl groups with the other componentsused in the preparation of polyesters. The polyester may be prepared byreacting a polycarboxylic acid or hydroxy carboxylic acid withpolyhydric alcohols. It is also possible to use a mixture of polyhydricalcohols and polyamines such as ethylenediamine, polyethylenediamine,1,4-butylenediamine and the like. Amines such as bis-(2-aminoethyl)ether or amino carboxylic acids such as glycine, alanine, valine,phenylalanine, hydroxyproline and the like may also be used. Thepolyesters may contain hetero atoms in addition to the ester groupsincluding oxygen, sulfur, nitrogen and the like in the chain. Moreover,the radicals making up the polyester may be either saturated orunsaturated and may contain double or triple bonds as well as modifyingradicals of saturated or unsaturated fatty acids such as oleic acid orfatty alcohols such as oleyl alcohol and the like.

Any suitable polycarboxylic acid may be used in the preparation of thepolyesters such as, for example, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaicacid, sebacic acid, brassylic acid, maleic acid, fumaric acid,glutaconic acid, alpha-hydromuconic acid, beta-hydromuconic acid,alpha-butyl-alpha-ethylglutaric acid, alpha,beta-diethyl-succinic acid,isophthalic acid, terephthalic acid, hemimellitic acid, trimelliticacid, trimesic acid, mellophanic acid, prehnitic acid, pyromelliticacid, benzenepentacarboxylic acid, l,4-cyclohexanedicarboxylic acid, andthe like. Any suitable polyhydric alcohol may be used in the preparationof the polyesters such as, for example, ethylene glycol, l,3-propyleneglycol, l,2-propylene glycol, l,4-butylene glycol, 1,3-butylene glycol,l,2-butylene glycol, l,5-pentanediol, l,4-pentanediol, l,3-pentanediol,l,6-hexanediol, l,7-heptanediol, glycerine, trimethylolpropane,1,3,6-hexanetriol, triethanolamine, pentaerythritol, sorbitol and thelike.

Any suitable polyhydric polyalkylene ether may be used as the activehydrogen containing'compound such as, for example, the condensationproduct of an alkylene oxide or of an alkylene oxide with a polyhydricalcohol. Any suitable polyhydric alcohol may be used such as thosedisclosed above for use in the preparation of the hydroxyl polyesters.Any suitable alkylene oxide may be used such as, for example, ethyleneoxide, propylene oxide, butylene oxide, amylene oxide, and the like. Ofcourse, the polyhydric polyalkylene ethers can be prepared from otherstarting materials such as, for example, tetrahydrofuran, epihalohydrinssuch as, for example, epichlorohydrin and the like as well as arlkyleneoxides such as, for example, styrene oxide and the like. The polyhydricpolyalkylene ethers may have either primary or secondary hydroxyl groupsand preferably are polyhydric polyalkylene ethers prepared from alkyleneoxides having from two to five carbon atoms such as, for example,polyethylene ether glycols, polypropylene ether glycols, polybutyleneether glycols and the like. It is often advantageous to employ sometrihydric or higher polyhydric alcohols such as glycerine,trimethylolpropane, pentacrythritol and the like in the preparation ofthe polyhydric polyalkylene ethers so that some branching exists in theproduct. Generally speaking, it is advantageous to condense from about 5to about 30 moles of alkylene oxide per functional group of thetrihydric or higher polyhydric alcohol. The polyhydric polyalkyleneethers may be prepared by any known process such as, for example, theprocess disclosed in l859 by Wurtz and in Encyclopedia of ChemicalTechnology, Volume 7, pages 257 to 262, published by IntersciencePublishers, Inc. i or in US. Pat. No. 1,922,459.

Any suitable polyhydric polythioether may be used such as, for example,the condensation product of thiodiglycol or the reaction product of apolyhydric alcohol such as is disclosed above for the preparation of thehydroxyl polyesters with any other suitable thioether glycol. Othersuitable polyhydric polythioethers are disclosed in US. Pat. No.2,862,972 and 2,900,368.

Any suitable polyhydric alcohol may be used as the active hydrogencontaining compound such as, for example, alkane diols such as, forexample, ethylene glycol, 1,3-propylene glycol, l,2-propylene glycol,l,4-butylene glycol, l,3-butylene glycol, 1,5pentanediol,l,4-butanediol, l,3-pentanediol, l.6- hexanediol, l,7-heptanediol,2,2-dimethyll ,3-propanediol, 1,8-octanediol and the like includingl,20-eicosanediol and the like; alkene diols suchas, for example,2-butene-l,4-diol, Z-pentene-l ,S-diol, 2-hexenel ,6-diol, Z-heptenel,7-diol and the like; alkyne diols such as, for example.2-butyne-l,4-diol, l,5'-hexadiyne-l,6-diol and the like; alkane triolssuch as, for example, l,3,6-hexanetriol, l,3,7-heptane triol,l,4,8-octane triol, l,6,l2-dodecane triol and the like; alkene triolssuch as 4-hexenel,3,6-triol and the like; alkyne triols such as2-hexyne-l,4,6-triol and the like; alkane tetrols such as, for example,l,2,5,6-hexane tetrol and the like; alkene tetrols such as, for example,3-heptene-l,2,6,7-tetrol and the like; alkyne tetrols such as, forexample, 4-octyne-l,2,7,8-tetrol and the like.

Any suitable aliphatic thiol including alkane thiols containingtwo ormore -SH groups may be used such as, for example 1,2-ethane dithiol,l,2-propane dithiol, l,3-propane dithiol, 1,6-hexane dithiol,l,3,6-hexane trithiol and the like; alkene thiols such as for example,2-butene-l,4-dithiol and the like; alkyne thiols such as, for example,3-hexyne-l,6-dithiol and the like.

Any suitable polyamine may be used including, for example, aromaticpolyamines such as, for example, p-amino aniline, l,5-diaminonaphthalene, 2,4diaminotoluene. 1,3,5-benzene triamine, l,2,3-ben2enetriamine, l,4,5,8-naphthalene tetramine and the like; aliphaticpolyamines such as, for example, ethylenediamine, l,3-propylenediamine,l,4-butylenediamine, 1,3-butylenediamine, diethylenetriamine,triethylene-tetramine, l,3,6-hexane triamine, l,3,5,7-heptane tetramineand the like; heterocyclic polyamines such as, for example, 2,6-diaminopyridine, 2,4-diamino-5-aminomethyl pyrimidine,2,5-diamino-l,3,4-thiadiazole, piperazine and the like.

One especially preferred group of amines useful for preparing polymersare polyamines having the primary amine groups thereof blocked byketimine or aldimine groups. The reaction of carbonyl compounds with theprimary amine groups can be illustrated as follows:

The useful carbonyl compounds may have the following theoreticalstructural formula when the blocked polyamine is mixed with thediisocyanate' and exposed to moisture, the freed aldehyde or ketone canbe easily removed from the reaction mixture. Examples of preferredcarbonyl compounds include such aldehydes and ketones as acetone, methylethyl ketone, methyl n-butyl ketone, methyl tert-butyl ketone, ethylisopropyl ketone, acetaldehyde, propionaldehyde, butyraldehyde,isobutyraldehyde, and the like (i.e. including hexanone and hexanal).The polyamines to be blocked preferably have the structure RI II;N(HRINmun, or umrmmnnn mi where R is a difunctional aliphatic group containingfrom 2-48 carbon atoms, R is an aliphatic group containing l-24 carbonatoms and n is an integer of from 0-20. Representative R radicals aremethyl, propyl, butyl, decyl, hcxadeeyl, hexenyl. octenyl, tridecenyl,octadecyl, undecynyl and the like. lnert or noninterfering groups suchas C l. nitro and the like may be present on R and/or R.

Any suitable reaction product of a phenol with an alkylene oxideyielding a compound containing active hydrogens may be used such as, forexample, those disclosed in US. Pat. No. 2,843,568, such as for example,the reaction product of hydroquinone with ethylene oxide to give apolyalkylene arylene ether glycol having a molecular weight above about750 or other polyalkylene arylene ether glycols disclosed in saidpatent.

Any suitable reaction product of a phenol-aldehyde resin with analkylene oxide may be used such as, for example, a novolac having theformula (HI 0 II R ll wherein n is l to 5 and R is a lower alkyl radicalsuch as methyl, ethyl, propyl, butyl, tertiary butyl and the likereacted with an alkylene oxide such as those disclosed above for thepreparation of the polyhydric polyalkylene ethers.

Any suitable reaction product of an amine with an alkylene oxide may beused such as, for example, the reaction product of an alkylene oxidewith a tolylenediamine such as, 2,4- tolylenediamine,2,6-tolylenediamine or the like, a diphenylmethane diamine such as4,4-diaminodiphenylmethane or the like, xylylene diamine, as well asalkylene diamines such as, for example, ethylenediamine,propylenediamine, l,4-butylenediamine, hexamethylenediamine l, lO-dodecane diamine.

Any suitable phenol may be used such as, for example, 2,2- bis(p-hydroxyphenyl)propane (bisphenol A) and the like.

Any suitable polyamide may be used such as, for example, those obtainedby reacting adipic acid with hexamethylene diamine and the like.

Any suitable polyacetal may be used such as, for example, the reactionproduct of formaldehyde or other suitable aldehydes with a polyhydricalcohol such as those disclosed above for use in the preparation of thehydroxyl polyester.

Other alcohol compounds which do not necessarily fit within any of thepreviously set forth classes of compounds and which nevertheless containactive hydrogen containing groups which are quite suitable for theproduction of the polymers are pentaerythritol, sorbitol,triethanolamine, mannitol,N,N,N'N'-tetrakis(Z-hydroxypropyl)ethylenediamine, as well as compoundsof any of the classes set forth above which are substituted with halogensuch as, for example, chloro, iodo, bromo and the like; nitro; alkoxy,such as, for example, methoxy, ethoxy, propoxy, butoxy and the like;carboalkoxy such as for example, carbomethoxy, carboethoxy and the like;dialkyl amino such as, for example, dimethylamino, diethylamino,dipropylamino, methylethylamino and the like; mercapto, carbonyl,thiocarbonyl, phosphoryl, phosphato and the like.

Other substances which can be used include natural substances such ascastor oil and the like.

The molar proportions of the diisocyanate and the compounds bearingZerewitinoff active hydrogen atoms can vary and the like includingwidely. Those skilled in the art can determine the proportions ofreactants best suited for a particular purpose. For example, when makingpolyurethane elastomers, one often uses approximately equimolar amountsof glycol and the diisocyanate. Preferably, the active hydrogencontaining compound will be used in a molar ratio to the diisocyanate ofl 10 to 10:1.

The polymers can be prepared by reacting the diisocyanate and the activehydrogen containing compound at subatmospheric, atmospheric orsuperatmospheric pressure. Atmospheric pressure is preferred. Thereaction can be operated over a wide range of temperatures. Thoseskilled in the art will recognize that there are great differences inthe relative reactivity of various groups containing active hydrogenatoms, amines reacting faster than alcohols, primary alcohols reactingfaster than tertiary alcohols-to name a few examples; accordingly, onewill select a temperature at which the reaction occurs at a rateconvenient for the purpose at hand.

Preferably, the reaction temperature ranges between about 20 and l50 C.However, the temperature is not critical.

If desired, the reaction may be carried out in an inert solvent.Representative solvents include tetrahydrofuran, odichlorobenzene,chlorobenzene, xylene, methyl isobutyl ketone, toluene and ethylacetate. In general, the solvent should be free fromisocyanate-reactable groups such as groups bearing Zerewitinoff-activehydrogen atoms.

In the preparation of the polymers, a portion of the diisocyanates (i.e.up to about 90 mole percent and preferably from 0 to 50 mole percent)can be replaced by known polyisocyanates. Representative of such knownpolyisocyanates are ethylenediisocyanate, hexamethylenediisocyanate,butylene- 1,3-diis0cyanate, ethylidene diisocyanate, butylidenediisocyanate, l ,2,4-butanetriisocyanate, 1,3,3-pentanetriisocyanate,p-phenylene-2,2 '-bis(ethylisocyanate l,4-naphthalene-2,2-bis(ethylisocyanate, S-chlorophenylenel,3-bis(propyl-3-isocyanate), tolylene diisocyanate,m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylene-4,4'-diisocyanate, xylylene-l,4-diisocyanate,4,4'-diphenylenemethanediisocyanate and the like. A particularlydesirable group of polyisocyanates to be employed in combination withthe instant diisocyanates in the preparation of the polymers are thosedescribed in the application of Rogier and Kamal, Ser. No. 250,21 l,filed Jan. 9, 1963, now US. Pat. No. 3,455,883 entitled Polyisocyanatesand Derivatives. These polyisocyanates are derived from polymeric fatacids and have the following idealized structural formula: 7

The polyisocyanates of the above fonnula wherein y is 0 are prepared byconverting the polymeric fat acids to the corresponding polymeric acidchlorides, reacting the acid EXAMPLE G A mixture of 2.00 g. of thecarbonate diisocyanate as prepared in Example D and 0.49 g. of thediketimine of diethylene triamine and methylisobutyl ketone was spreadon glass with a 3-mil drawdown bar. The film became tack free on thesurface in l2 minutes and thoroughly dry in l hour at 77 F. and 74percent relative humidity. The coating was of good rance. appea EXAMPLESH AND I Coatings are prepared as in example G using the diisocyanates ofexamples E and F. Similar results are obtained. Where desired, elevatedtemperatures and/or catalysts such as dibutyl tin dilaurate can be usedto accelerate the cure of the polymers.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A dinitrile having the formula:

' where n is 5 to 20. m is 0 to 15 and the sum of n and m is 14 to 2.The dinitrile ofclaim 1 wherein the sum ofn and m is 16. 3. Thedinitrile ofclaim 1 wherein n is 9.

4. The dinitrile ofclaim 3 wherein m is 7.

5. The dinitrile of claim I wherein n is 7.

6. The dinitrile of claim I wherein n is 6.

7. The dinitrile of claim 1 wherein m is 10.

8. The dinitrile of claim 1 wherein m is 8.

=8 i l t

2. The dinitrile of claim 1 wherein the sum of n and m is
 16. 3. Thedinitrile of claim 1 wherein n is
 9. 4. The dinitrile of claim 3 whereinm is
 7. 5. The dinitrile of claim 1 wherein n is
 7. 6. The dinitrile ofclaim 1 wherein n is
 6. 7. The dinitrile of claim 1 wherein m is
 10. 8.The dinitrile of claim 1 wherein m is
 8. 20.